Electrode for lithium-ion secondary battery and manufacturing method thereof, and lithium-ion secondary battery

ABSTRACT

A highly reliable electrode for a lithium-ion secondary battery is provided. A highly reliable lithium-ion secondary battery is also provided using the electrode for a lithium-ion secondary battery. The electrode for a lithium-ion secondary battery includes a current collector and an active material layer. The active material layer includes an active material, graphene, and polyimide. The active material includes a plurality of nanowires each of which grows with a silicon particle used as a nucleus and extends in one direction into a fine needle. The graphene includes a region in contact with the plurality of nanowires, and polyimide includes a region in contact with the graphene. The lithium-ion secondary battery uses the electrode as a negative electrode.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to an object, a method, or a manufacturingmethod. In addition, the present invention relates to a process, amachine, manufacture, or a composition of matter. In particular, oneembodiment of the present invention relates to a power storage device, adriving method thereof, or a manufacturing method thereof. Moreparticularly, one embodiment of the present invention relates to anelectrode for a lithium-ion secondary battery, a manufacturing methodthereof, and a lithium-ion secondary battery.

2. Description of the Related Art

In recent years, portable electronic devices such as smartphones andtablets have spread rapidly. Also with growing interest in theenvironment, hybrid cars and electric cars have attracted attention,thereby increasing the importance of secondary batteries typified bylithium-ion secondary batteries.

The basic structure of a secondary battery includes a positiveelectrode, a negative electrode, and an electrolyte (an electrolytesolution or a solid electrolyte) provided therebetween. Typically, thepositive electrode and the negative electrode each include a currentcollector and an active material provided over the current collector. Inthe case of a lithium-ion secondary battery, a material capable ofreceiving and releasing lithium ions is used as an active material forapositive electrode and a negative electrode.

A negative electrode used in such a secondary battery (hereinafterreferred to as a “negative electrode for a secondary battery”) ismanufactured in such a manner that a layer containing an active material(hereinafter referred to as an “active material layer”) is formed over asurface of a current collector. A conventional material used as anegative electrode active material is black lead which can receive andrelease ions serving as carriers (hereinafter referred to as “carrierions”). That is, the negative electrode is fabricated as follows: blacklead which is a negative electrode active material, carbon black as aconductive additive, and a resin as a binder are mixed to form slurry,and the slurry is applied to a current collector and dried.

In contrast, in the case where silicon or silicon doped with phosphorusor boron is used as a negative electrode active material, carrier ionsabout four times as much as those in the case of using carbon can bereceived, and the theoretical capacity of a silicon negative electrodeis 4200 mAh/g, which is significantly higher than that of a carbon(black lead) negative electrode, 372 mAh/g. For this reason, silicon isan optimal material for increasing the capacity of a secondary battery,and secondary batteries using silicon as a negative electrode activematerial have been actively developed in order to increase the capacity.

However, an increase in the number of received carrier ions increasesthe amount of change in the volume of silicon due to reception andrelease of carrier ions in charge and discharge cycles, resulting inlower adhesion between a current collector and silicon and deteriorationof battery characteristics due to charge and discharge. Furthermore, insome cases, silicon is deformed and broken to be separated orpulverized, which causes a serious problem of a battery malfunction.

In view of this, the following way has been proposed: a layer containingsilicon is formed over a negative electrode current collector and alayer containing graphite is formed over the layer containing silicon sothat expansion arid contraction of the layer containing siliconinfluences less on degradation of battery characteristics (see PatentDocument 1).

REFERENCE Patent Document

Patent Document 1 Japanese Published Patent Application No. 2001-283834

SUMMARY OF THE INVENTION

However, in Patent Document 1, regardless of whether a negativeelectrode active material layer has a columnar shape or a powder form,when charge and discharge are repeated more than 10 cycles as describedin the document, expansion and contraction of the volume cannot beavoided as long as the negative electrode active material receives andreleases carrier ions. Therefore, deformation and breakage of thenegative electrode active material layer cannot be prevented, so thatthe reliability of a battery is difficult to maintain.

In particular, in the case where silicon in the form of a columnarstructure body is used as a negative electrode active material, thecolumnar structure body might be separated from a current collector inrepeated charge and discharge, and the charge and discharge capacity andthe discharge rate might be significantly reduced with an increase inthe number of cycles. This is because of expansion and contraction of aentire columnar structure body.

In view of the above problems, an object of one embodiment of thepresent invention is to provide a Highly reliable electrode for alithium-ion secondary battery. Another object is to provide a highlyreliable lithium-ion secondary battery with use of flic electrode for alithium-ion secondary battery. Still another object is to provide anovel power storage device.

An object of one embodiment of the present invention is to achieve atleast one of the aforementioned objects.

One embodiment of the present invention is an electrode including acurrent collector and an active material layer. The active materiallayer includes an active material, graphene, and polyimide. The activematerial includes a plurality of nanowires each of which grows with asilicon particle used as a nucleus and extends in one direction into afine needle The graphene includes a region in contact with the pluralityof nanowires, and polyimide includes a region in contact with thegraphene.

Graphene refers to a one-atom-thick sheet of carbon molecules having sp²bonds. Graphene includes single-layer graphene and multilayer graphene.Graphene may contain oxygen at a concentration of 2 atomic % to 11atomic %, preferably 3 atomic % to 10 atomic %.

One embodiment of the present invention is a lithium-ion secondarybattery including at least a positive electrode and a negativeelectrode. The negative electrode includes a negative electrode currentcollector and a negative electrode active material layer. The negativeelectrode active material layer includes a negative electrode activematerial, a first graphene, and polyimide. The negative electrode activematerial includes a plurality of nanowires each of which grows with asilicon particle used as a nucleus and extends in one direction into afine needle. The first graphene includes a region in contact with theplurality of nanowires and polyimide includes a region in contact withthe first graphene. The positive electrode includes a positive electrodecurrent collector and a positive electrode active material layer. Thepositive electrode active material layer includes a positive electrodeactive material, a second graphene, and polyvinylidene fluoride. Thesecond graphene includes a region in contact with the positive electrodeactive material.

One embodiment of the present invention is a method for manufacturing anelectrode for a lithium ion secondary battery, which includes the stepsof mixing silicon particles and graphene oxide; mixing the mixture ofsilicon particles and graphene oxide with a mixed solution of apolyimide precursor and a polar solvent, thereby obtaining slurry; andapplying the slurry to a current collector and then performing baking.As a result, a nanowire grows with a silicon panicle used as a nucleusand extends in one direction into a fine needle, graphene oxide isreduced to graphene, and the polyimide precursor is imidized to bepolyimide.

According to one embodiment of the present invention, deformation andbreakage of silicon can be prevented even when the volume of siliconchanges with reception and release of carrier ions, resulting inincreased reliability of an electrode for a lithium-ion secondarybattery. In addition, a lithium-ion secondary battery including theelectrode can have improved reliability.

BRIEF DESCRIPTION OF THE DRAWINGS

In the accompanying drawings:

FIG. J illustrates a method for manufacturing an electrode for alithium-ion secondary battery;

FIGS. 2A and 2B illustrate a negative electrode;

FIGS. 3A to 3C illustrate a positive electrode;

FIGS. 4A to 4C illustrate lithium-ion secondary batteries;

FIGS. 5A to 5C illustrate an electric device; and

FIG. 6 is a SEM photograph of an electrode for a lithium-ion secondarybattery.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, embodiments and example will be described with reference todrawings. Note that the embodiments and the example can be implementedin many different modes, and it will be readily appreciated by thoseskilled in the an that modes and details thereof can be changed invarious ways without departing from the spirit and scope of the presentinvention. Thus, the present invention should not be interpreted asbeing limited to the following descriptions of the embodiments and theexample.

Note that in the structures of the present invention described below,the same portions or portions having similar functions arc denoted bythe same reference numerals in different drawings, and descriptionthereof is not repeated. Furthermore, the same hatching pattern is usedto denote portions having similar functions, and the portions are notespecially denoted by reference numerals in some cases.

Embodiment 1

In this embodiment, a method for manufacturing an electrode for alithium-ion secondary battery of one embodiment of the present inventionwill be described with reference to FIG. 1.

FIG. 1 is a flowchart showing the method for manufacturing an electrodefor a lithium-ion secondary battery of one embodiment of the presentinvention. First, an active material, a conductive additive, and ahinder are prepared. In this embodiment, silicon, graphene, andpolyimide are used as the active material, the conductive additive, andthe binder, respectively.

First, as shown in step S11, silicon particles, graphene oxide, apolyimide precursor, and a polar solvent are mixed to prepare slurry. Inthis embodiment, silicon:graphene oxide:polyimide=40:40:20 (wt %) issatisfied.

Silicon particles are used as silicon. Silicon particles preferably havean average diameter of 10 nm to 1 μm.

Silicon is mixed with the polar solvent first. As the polar solvent, NMP(also referred to as N-methylpyrrolidone, 1-methyl-2-pyrrolidene, orN-methyl-2-pyrrolidone), dimethylformamide, or the like can be used. Inthis embodiment, NMP is used as the polar solvent.

Then, graphene oxide and NMP are added to the mixture of siliconparticles and NMP and further mixed.

In the case where graphene is used as the conductive additive, it Lspreferable to use reduced graphene oxide (RGO) obtained by reducinggraphene oxide. Graphene oxide can be produced by a Hummers method, amodified Hummers method, or the like. Note that the method for formingan electrode for a lithium-ion secondary battery of one embodiment ofthe present invention is not limited by the degree of separation ofgraphene oxide.

For example, in the Hummers method, graphite such as flake graphite isoxidized to give graphite oxide. Obtained graphite oxide is graphitethat is oxidized in places and thus to which a functional group such asan epoxy group, a carbonyl group, a carboxyl group, or a hydroxyl groupis bonded. In the graphite oxide, the crystallinity of graphite is lostand the distance between layers is increased. Therefore, graphene oxidecan be easily obtained by separation of the layers from each other byultrasonic treatment or the like.

The length of one side (also referred to as a flake size) of thegraphene oxide is greater than or equal to 50 nm and less than or equalto 100 μm, preferably greater than or equal to 800 nm and less than orequal to 20 μm. In the case where the flake size is smaller than theaverage diameter of active material particles, the surface contact withthe active material particles and the connection between graphene flakesare less likely to be made, resulting in difficulty in increasing theelectric conductivity of an active material layer.

As the average diameter of silicon particles decreases, the particleshave higher cohesive energy and thus are less likely to be disperseduniformly in slurry. This produces locally a dense area where siliconpanicles are aggregated and a sparse area where silicon particles arenot aggregated, resulting in reduced proportion of active materialscontributing to electron conduction.

Graphene or reduced graphene is less likely to be dispersed in slurrythan graphene oxide; therefore, the use of graphene or reduced graphenein the production of slurry causes aggregation of graphene in theslurry. This is because graphene or reduced graphene has no functionalgroup contributing to dispersion in the slurry. The aggregation ofgraphene tends to interrupt the formation of the conductive path with anactive material, reducing the proportion of active materialscontributing to electron conduction. Hence, in the area of an electrodewhere aggregated silicon particles are not m contact with graphene,silicon does not contribute to the discharge capacity of a battery.

In view of the above, to prevent the aggregation of silicon particlesand the aggregation of graphene oxide, silicon and graphene oxide arepreferably mixed using a polar solvent so that a thick paste isobtained. Oxygen in the functional group in graphene oxide is negativelycharged in a polar solvent; hence, aggregation of graphene oxide is lesslikely to occur but graphene oxide strongly interacts with the polarsolvent such as NMP. Thus, the functional group such as an epoxy groupin the graphene oxide interacts with the polar solvent, which probablyprevents aggregation of graphene oxide, resulting in uniform dispersionof graphene oxide in slurry.

Next, a binder is added to the mixture of silicon particles and grapheneoxide. The binder is added to the mixture in which graphene oxide isuniformly dispersed to be in contact with a plurality of siliconparticles; as a result, graphene oxide can be bonded to the siliconparticles while maintaining the dispersed state. The binder is notnecessarily added depending on the compounding ratio between silicon andgraphene oxide; however, the addition of the binder increases thestrength of the electrode.

As the binder, polyvinyldene fluoride (PVDF) as well as polyimide can beused, for example. Note that the binder added in this step is a mixedsolution of a polyimide precursor and a polar solvent (e.g., NMP), andthe polyimide precursor is imidized to be polyimide by a baking processin step S14. The mixed solution of the polyimide precursor and the polarsolvent has a pH of 2 to 4.

Then, a polar solvent is added to the mixture until the mixture haspredetermined viscosity and the polar solvent and the mixture am mixed;thus, the slurry can be prepared. In this step, the mixing and theaddition of the polar solvent may be repeated more than once.

Through the above steps, the slurry in which the active material,graphene oxide, and the binder are uniformly dispersed can be obtained.

In the preparation of the slurry in this embodiment, the compoundingratio of the active material to graphene oxide and the binder is40:40:20; however, one embodiment of the present invention is notlimited hereto. For example, the compounding ratio of silicon particlesto graphene oxide and polyimide may be 30:20:50 to 95:1:4.Alternatively, the compounding ratio can be changed as appropriate inthe following range: 30% to 95% of silicon particles: 1% to 50% ofgraphene oxide; and 4% to 60% of polyimide.

Then, as shown in step S12, the slurry is provided on either or bothsides of a current collector. The slurry can be provided by a rollcoating method using an applicator roll or the like, a screen printingmethod, a doctor blade method, or a coating method such as a spincoating method or a bar coating method.

The current collector can be formed using a material that has highelectric conductivity and is not alloyed with a carrier ton of lithiumor the like, such as a metal typified by stainless steel, iron, copper,titanium, and nickel, or an alloy thereof.

Note that an undercoat may be applied to the current collector beforethe slurry is provided on the current collector. The application of theundercoat to the current collector reduces the interface resistancebetween the current: collector and an active material layer formedlater, and/or increases the adhesion between the active material layerand the current collector. Note that if there is no problem with theadhesion between the current collector and the active material layer,the electrode strength, and the interface resistance between the currentcollector and the electrode, it is not necessary to apply the undercoatto the current collector.

Next, as shown in step S13, the slurry formed over the current collectoris dried by a method such as ventilation diving or reduced pressure(vacuum) drying to form the active material layer. The drying ispreferably performed using a hot wind with temperatures of 50° C. to180° C., for example, at 80° C. for two hours. Through this step, thepolar solvent contained in the active material layer is evaporated. Notethat there is no particular limitation on the atmosphere.

The active material layer may be pressed by a compression method such asa roll press method or a flat plate press method to be consolidated.When the pressing is performed while being heated at higher than orequal to 90° C. and lower than or equal to 180° C. preferably lower thanor equal to 120° C. the binder (e.g., polyimide) contained in theundercoat or the active material layer is softened to such an extentthat the characteristics of the electrode is not changed, furtherincreasing the adhesion between the current collector and the activematerial layer.

Next, as shown in step S14, the electrode with the dried slurry isbaked.

The baking of the electrode with the dried slurry is preferablyperformed in a vacuum furnace/ For example, the degree of vacuum in thevacuum furnace is preferably 2×10⁻² [Pa].

The electrode with the dried slurry is preferably baked at temperaturesgradually increasing to the maximum temperature, which can be determineddepending on the upper temperature limit of the binder. In thisembodiment, the maximum temperature is, for example, higher than orequal to 360° C. and lower than or equal to 400° C. at which thepolyimide precursor is imidized. For example, the dried electrode isbaked as follows: the temperature is raised from room temperature toapproximately 100° C. and baking is performed for a certain period; thetemperature is raised from approximately 100° C. to approximately 200°C. and baking is performed for a certain period; the temperature israised from approximately 200° C. to approximately 250° C. and baking isperformed for a certain period; and the temperature is raised fromapproximately 250° C. to approximately 370° C. and baking is performedfor a certain period. Lastly, the temperature is lowered to roomtemperature.

The baking of the electrode produces a nanowire that grows with asilicon particle used us a nucleus and extends in one direction into afine needle. The nanowire has a diameter of approximately severalnanometers to several tens of nanometers and a length of severalmicrometers to several tens of micrometers. The silicon nanowire growswith a silicon particle as a nucleus; accordingly, the diameter of thesilicon nanowire is smaller than that of the silicon particle in somecases. In addition, generated nanowires are tangled, so that a networkof silicon nanowires is obtained. It is thus possible to produce anactive material including a plurality of nanowires each of which growswith a silicon particle used as a nucleus and extends in one directioninto a fine needle. Note that silicon particles used as nuclei ofnanowires may be locally clumped or aggregated.

In the case where silicon particles am used as an active material, thesilicon particles expand and contract in all directions when siliconreceives and releases carrier ions. This easily causes deformation andbreakage of silicon particles, thereby making it difficult to maintainthe reliability of the electrode. The deformation and breakage ofsilicon particles produces another film on the surface of siliconparticles, and irreversible capacity is generated by the film, as aresult, part of discharge capacity is lost. When the lithium-ionsecondary battery is repeatedly charged and discharged in that state,the capacity is reduced. The reduction in capacity due to the repeatedcharge and discharge leads to a reduced charge-discharge efficiency ofthe lithium-ion secondary battery.

In contrast, a silicon nanowire tends to expand in the direction of thediameter but not to expand in the direction of the axis even when thesilicon nanowire receives and releases lithium. In other words, a changein the volume of the silicon nanowire in expansion and contraction isdirection dependent, therefore, silicon deformation and breakage is notlikely to occur, leading to improved reliability of the electrode.Furthermore, another film is prevented from being formed on the surfaceof silicon particles, which inhibits generation of irreversible capacityand a reduction in discharge capacity. A reduction in the capacity ofthe lithium-ion secondary battery can also prevented, thereby increasingthe charge-discharge capacity of the lithium-ion secondary battery.

In the baking of the electrode, graphene can be formed by reducinggraphene oxide. Here, oxygen in graphene oxide is not necessarilyentirely extracted and may remain partly in the graphene. In the casewhere graphene contains oxygen, the proportion of oxygen in the graphenemeasured by XPS is higher than or equal to 2 atomic % and lower than orequal to 20 atomic %, preferably higher than or equal to 3 atomic % andlower than or equal to 15 atomic %. Because graphene oxide is uniformlydispersed in the slurry, reduced graphene is also uniformly dispersed inthe active material of the electrode. The graphene is formed so as tocover the nanowires that grow with silicon particles as nuclei and arctangled. The graphene has a planar shape and therefore touches a largearea of the tangled nanowires. This reduces the contact resistancebetween the nanowires and the graphene to reduce the resistance of theelectrode.

Furthermore, in the baking of the electrode, a polyimide precursor isimidized to be polyamide. The polyimide precursor is added whilegraphene oxide is uniformly dispersed to be in contact with a pluralityof silicon particles in the production of the slurry. Hence, after thebaking of the electrode, the tangled nanowires are covered with grapheneand polyimide is further provided to maintain that state. Accordingly,deformation and breakage of silicon can be further prevented even whenthe nanowires expand and contract.

The baking of the electrode cannot be performed at temperatures higherthan or equal to the upper temperature limit of the binder. For example,in the case where PVDF is used as a binder, the baking of the electrodeneeds to be performed at temperatures lower than 170° C. In the casewhere the baking of the electrode is performed at temperatures lowerthan 170° C., the electrode needs to be heated for at least ten hours inorder to reduce graphene oxide sufficiently. In contrast, when polyimideis used as a binder, heat treatment can be performed at a highertemperature than that in the case of using PVDF because a polyimideprecursor is imidized at 270° C. to 400° C. In addition, graphene oxidecan be reduced in a shorter time than that in the case of using PVDF.

In one embodiment of the present invention, production of nanowiresusing silicon particles as nuclei, reduction of graphene oxide toproduce graphene, and imidization of a polyimide precursor can beperformed in the step of baking slurry. As a result, the number ofproduction steps can be reduced in the manufacture of electrodes.

Lastly, as shown in step S15, the baked electrode is stamped into adesired shape, whereby an electrode for a lithium-ion secondary batteryis completed.

In the flowchart of FIG. 1, the reduction of graphene oxide and thebaking of the electrode are performed at the same time; however, oneembodiment of the present invention is not limited to this case. Forexample, after the drying step of the electrode in step S13, graphenemay be produced by chemical reduction of graphene oxide, and then theelectrode may be baked. In this specification and the like, chemicalreduction of graphene oxide refers to reduction by a chemical reactionusing a reducing agent.

With reaction of graphene oxide using a reducing solution, the grapheneoxide included in the active material layer is reduced to graphene. Thisreduction treatment is preferably performed at temperatures of roomtemperature to 150° C., more preferably at temperatures of roomtemperature to 80° C. The reduction time of the graphene oxide can belonger than or equal to 3 minutes and shorter than or equal to 10 hours.

Examples of the reducing solution include ascorbic acid, hydrazine,dimethyl hydrazine, hydroquinone, sodium boron hydride (NaBH₄), tetrabutyl ammonium bromide (TBAB), lithium aluminium hydride (LiAlH₄).N,N′-diethylhydroxylamine, and a derivative thereof. For example,ascorbic acid and hydroquinone are preferable to hydrazine and sodiumboron hydride in that they are safe owing to low reducing ability andutilized industrially with ease.

A polar solvent can be used as the solvent in the reducing solution. Anymaterial can be used for the polar solvent as long as it can dissolvethe reducing agent. Examples of the polar solvent include water,methanol, ethanol, acetone, tetrahydrofuran (THF), dimethylformamide(DMF), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethyleneglycol, diethylene glycol, and glycerin, and a mixed solution of any twoor more of the above.

The pH of the reducing solution is, for example, greater than or equalto 4 and less than 11, preferably greater than or equal to 5 and lessthan or equal to 7. To control the pH of the reducing solution, thereducing solution preferably contains a pH adjuster. Any kind ofalkaline solution or alkaline salt can be used as the pH adjuster; forexample, sodium hydroxide, potassium hydroxide, calcium hydroxide,lithium hydroxide, ammonium hydroxide, sodium carbonate, potassiumcarbonate, calcium carbonate, or lithium carbonate can be used.

As the reducing solution, a mixed solution of ethanol and ascorbic acid,or a mixed solution of water, ascorbic acid, and lithium hydroxide canbe used.

Protons are added to graphene oxide by ascorbic acid when an activematerial layer formed over a current collector is soaked in a reducingsolution. Then, the graphene oxide is reduced by the release of H₂O,whereby graphene is probably formed. The reduction of graphene oxide inthe reducing solution can inhibit release of carbon from graphene.

After the chemical reduction, the current collector over which theactive material layer is formed is washed and then dried. The washing ofthe current collector over which the active material layer is formed ispreferably performed using a solution given as the solvent contained inthe reducing solution. The solution may be either the same as ordifferent from the solvent contained in the reducing solution. Thedrying is preferably performed in a reduced pressure (vacuum) atmosphereor a reduction atmosphere. For example, this drying step may beperformed at temperatures of 50° C. to 200° C. for 1 hour to 48 hours.The drying allows sufficient evaporation or removal of the polar solventand moisture in the active material layer The drying step can alsofacilitate the reduction of graphene oxide.

After that, the electrode is baked, thereby producing nanowires usingsilicon particles as nuclei, and imidizing polyimide.

Through the above steps, the electrode for a lithium-ion secondarybattery of one embodiment of the present invention can be manufactured.

One embodiment of the present invention can be implemented inappropriate combination with any of the other embodiments.

Embodiment 2

In this embodiment, a lithium-ion secondary buttery and a manufacturingmethod thereof will be described with reference to FIGS. 2A and 2B,FIGS. 3A to 3C, arid FIGS. 4A to 4C.

First, a negative electrode that can be used tor a lithium-ion secondarybattery will be described with reference to FIGS. 2A and 2B.

FIG. 2A is a perspective view of a negative electrode 410, and FIG. 2Bis a cross-sectional view of the negative electrode 410. The negativeelectrode 410 includes, for example, a negative electrode currentcollector 411 and a negative electrode active material layer 412 whichis formed over the negative electrode current collector 411 by a coatingmethod, a CVO method, a sputtering method, or the like, FIGS. 2A and 2Billustrate an example where an undercoat 413 is provided between thenegative electrode current collector 411 and the negative electrodeactive material layer 412; however, the undercoat 413 is not necessarilyprovided. FIG. 2A illustrates an example where the negative electrodeactive material layer 412 is provided over one surface of the negativeelectrode current collector 411 with a sheet shape (or a strip-likeshape); however, one embodiment of the present invention is not limitedto this example. The negative electrode active material layers 412 maybe provided so that the negative electrode current collector 411 issandwiched therebetween. Also in FIG. 2A, the negative electrode activematerial layer 412 is provided over the whole negative electrode currentcollector 411; however, the negative electrode active material layer 412may be provided over part of the negative electrode current collector411. For example, it is preferable that the negative electrode activematerial layer 412 not be provided in a portion where the negativeelectrode current collector 411 is connected to a negative electrodetab.

The negative electrode current collector 411 can be formed using amaterial that has high electric conductivity and is not alloyed with acarrier ion of lithium or the like, such as a metal typified bystainless steel, iron, copper, titanium, or nickel or an alloy thereof.The negative electrode current collector 411 can have a foil-like shape,a plate-like shape (sheet-like shape), a net-like shape, apunching-metal shape, an expanded-metal shape, or the like asappropriate. The negative electrode current collector 411 preferably hasa thickness of 6 μm to 30 μm.

A material with which lithium can be dissolved and precipitated or amaterial into/from which lithium ions can be inserted and extracted canbe used for the negative electrode active material; for example, it ispossible to use a lithium metal, a carbon-baaed material, or analloy-based material as well as the .silicon nanowire of one embodimentof the present invention.

In FIG. 2B, the negative electrode active material includes a pluralityof nanowires each of which grows with a silicon particle used as anucleus and extends in one direction into a fine needle. The pluralityof nanowires are tangled.

In the case where the negative electrode active material layer 412 isformed by a coating method, as illustrated in FIG. 1, a conductiveadditive or a binder is added to the negative electrode active materialto form a negative electrode paste; and the negative electrode paste isapplied to the negative electrode current collector 411 and dried.

The negative electrode active material layer 412 may be predoped withlithium. For the predoping, a lithium layer may be formed on a surfaceof the negative electrode active material layer 412 by a sputteringmethod. Alternatively, the negative electrode active material layer 412can be predoped with lithium by providing lithium foil on the surface ofthe negative electrode active material layer 412,

Examples of the conductive additive include carbon black such asacetylene black (AB) or ketjen black (KB), graphite (black lead)particles, and carbon nanotubes. Here, graphene is used as theconductive additive. Note that graphene also serves as an activematerial in some cases.

Graphene includes single-layer graphene and multilayer graphene.Graphene has a sheet-like shape with a length of several micrometers.

Single-layer graphene refers to a one-atom-thick sheet of carbonmolecules having sp² bonds and is very thin. Single-layer graphenecontains six-membered rings each composed of carbon atoms, which areconnected in the planar direction, and poly-membered rings each formedwhen a carbon-carbon bond in part of a six-membered ring is broken, suchas a seven-membered ring, an eight-membered ring, a nine-membered ring,and a ten-membered ring.

Note that the poly-membered ring is composed of carbon and oxygen atomsin some cases. An oxygen atom is sometimes bonded to a carbon atom inthe poly-membered ring. In the case where graphene contains oxygen, acarbon bond in part of a six-membered ring is broken, and an oxygen atomis bonded to a carbon atom whose bond is broken, whereby thepoly-membered ring is formed. Therefore, the bond of carbon arid oxygenhas an opening functioning as a path through which ions can transfer.Thus, as the proportion of oxygen included in the graphene is higher,the proportion of the openings each functioning as a path through whichions can transfer is increased.

In the case where graphene contains oxygen, the proportion of oxygen inthe graphene measured by XPS is higher than or equal to 2 atomic % andlower than, or equal to 11 atomic %, preferably higher than or equal to3 atomic % and lower than or equal to 10 atomic %. The conductivity ofthe graphene increases as the proportion of oxygen is lower. As theproportion of oxygen is higher, more openings serving as paths of ionscan be formed in the graphene.

In the case where the graphene is multilayer graphene, the grapheneincludes plural sheets of single-layer graphene, typically, 2 to 100sheets of single-layer graphene and is thus very thin. Since thesingle-layer graphene contains oxygen, the interlayer distance betweengraphenes is greater than or equal to 0.34 nm and less than or equal to0.5 nm. preferably greater than or equal to 0.38 nm and less than orequal to 0.42 nm, and more preferably greater than or equal to 0.39 nmand less than or equal to 0.41 nm. In general graphite, the interlayerdistance between single-layer graphenes is 0.34 nm. Since the interlayerdistance in the graphene is longer than that in general graphite, ionscan easily transfer in the direction parallel to a surface of thesingle-layer graphene. In addition, the graphene contains oxygen and isa single-layer graphene or a multilayer graphene containingpoly-membered rings and thus include openings in places. Therefore, inthe case where the graphene is multilayer graphene, ions can transfer inthe direction parallel to a surface of the single-layer graphene, i.e.,through a gap between the single-layer graphenes, and in the directionperpendicular to a surface of the graphene, i.e., through the openingsin the single-layer graphenes.

When a surface of the active material is in contact with an electrolytein a lithium-ion secondary battery, the electrolyte and the activematerial react with each other, so that a film is formed on the surfaceof the active material. The film is probably necessary for relievingreaction between the active material and the electrolyte and forstabilization. However, when the thickness of the film is increased,carrier ions arc less likely to be inserted in an electrode, leading toa reduction in the conductivity of lithium ions between the activematerial and the electrolyte and a waste of the electrolyte. In order tosolve these problems, the active material (here, nanowires each of whichgrows with a silicon particle used as a nucleus and extends in onedirection into a fine needle) is covered with graphene, therebypreventing an increase in the thickness of the film, a reduction in theconductivity of lithium ions, and a waste of the electrolyte.

It is said that the diffusion coefficient of lithium ions in silicon isapproximately 1×10⁻¹⁴ cm²/sec, which is lower than that in black lead,higher than or equal to 1×10⁻⁶ cm²/sec and lower than or equal to1×10⁻¹² cm²/sec. However, black lead used as an active material has asize of several micrometers, lithium ions therefore move a longdistance. The silicon nanowire of one embodiment of the presentinvention has a diameter of several nanometers to several tens ofnanometers although having a length of several micrometers to severaltens of micrometers. Accordingly, even when the diffusion coefficient islower than that in black lead, lithium ions move a shorter distance inthe silicon nanowire; hence, lithium ions can be inserted and extractedin a shorter time.

Silicon has a lower electric conductivity than carbon, and thus anegative electrode in which silicon is used as an active material has ahigh resistance. However, because graphene has a high electricconductivity, covering silicon with graphene enables electrons totransfer at a higher speed in the graphene through which lithium ionspass. In addition, graphene has a region in contact with a plurality ofsilicon nanowires. Because graphene has a thin sheet-like shape,covering the plurality of nanowires with graphene can increase thesilicon content in the active material layer and makes transfer oflithium ions easier than in graphite. As a result, the conductivity oflithium ions can be increased, reaction between silicon that is anactive material and lithium ions can be increased, and lithium ions canbe easily inserted in silicon.

The nanowire, which grows with a silicon particle, a negative electrodeactive material used as a nucleus and extends in one direction into afine needle, tends to expand in the direction of the diameter but not toexpand in the direction of the axis even when receives lithium. In otherwords, a change in the volume of the nanowire is direction dependent;therefore, silicon deformation and breakage is not likely to occur,improving the reliability of the electrode. Furthermore, another film isprevented from being formed on the surface of silicon, which preventsgeneration of irreversible capacity and a reduction in dischargecapacity.

In the case where silicon is used as a negative electrode activematerial, the material of a binder is preferably mechanically strong andclastic because the following is desirable, a negative electrode activematerial layer maintains its strength even when silicon expands andcontracts due to reception and release of lithium in changing anddischarging, and the negative electrode active material layer isdeformed with a change in the shape of silicon. Polyimide is preferablyused as such a binder. In the negative electrode of one embodiment ofthe present invention, the tangled nanowires are covered with grapheneand polyimide is further provided to maintain such a state. Accordingly,polyimide includes a region in contact with at least graphene, and mayinclude a region in contact with silicon nanowires.

By using the aforementioned electrode of one embodiment of the presentinvention as the negative electrode, the lithium-ion secondary batterycan be charged and discharged at a high rate.

Next, a positive electrode that can be used for a lithium-ion secondarybattery will be described with reference to FIGS. 3A to 3C.

FIG. 3A is a perspective view of a positive electrode 400, and FIG. 3Bis a cross-sectional view of the positive electrode 400. The positiveelectrode 400 includes, for example, a positive electrode currentcollector 401 and a positive electrode active material layer 402 that isformed over the positive electrode current collector 401 by a coatingmethod, a CVD method, a sputtering method, or the like. An undercoat 403is provided between the positive electrode current collector 401 and thepositive electrode active material layer 402. FIG. 3A illustrates anexample where the positive electrode active material layer 402 isprovided over one surface of the positive electrode current collector401 with a sheet shape (or a strip-like shape); however, one embodimentof the present invention is not limited to this example. The positiveelectrode active material layers 402 may be provided so that thepositive electrode current collector 401 is sandwiched therebetween.Also in FIG. 3A, the positive electrode active material layer 402 isprovided over the whole positive electrode current collector 401;however, the positive electrode active material layer 402 may beprovided over part of the positive electrode current collector 401. Forexample, it is preferable that the positive electrode active materiallayer 402 not be provided in a portion where the positive electrodecurrent collector 401 is connected to a positive electrode tab.

The positive electrode current collector 401 can be formed using amaterial that has high electric conductivity and is not alloyed with acarrier ion of lithium or the like, such as a metal typified bystainless steel, gold, platinum, zinc, iron, copper, aluminum, ortitanium, or an alloy thereof. Alternatively, an aluminum alloy to whichan element that improves heat resistance, such as silicon, titanium,neodymium, scandium, or molybdenum, is added can be used. Stillalternatively, a metal element that forms silicide by reacting withsilicon can be used. Examples of the metal element that forms silicideby reacting with silicon include zirconium, titanium, hafnium, vanadium,niobium, tantalum, chromium, molybdenum, tungsten, cobalt, arid nickel.The positive electrode current collector 401 can have a foil-like shape,a plate-like shape (sheet-like shape), a net-like shape, apunching-metal shape, an expanded-metal shape, or the like asappropriate. The negative electrode current collector 401 preferably hasa thickness of 10 μm to 30 μm.

Examples of the undercoat include a mixture of acetylene black (AB) andsodium polyacrylate (PAA) and a mixture of AB and PVDF. The compoundingratio of black lead to PAA is preferably 95:5 to 50:50 and thecompounding ratio of AB to PVDF is preferably 70:30 to 50:50.

FIG. 3C is a schematic view illustrating a longitudinal cross section ofthe positive electrode active material layer 402. The positive electrodeactive material layer 402 includes positive electrode active materialparticles 404, graphene 405 as a conductive additive, and a binder 406.

Examples of the conductive additive include acetylene black (AB), ketjenblack, graphite (black lead) panicles, and carbon nanotubes. Here, thepositive electrode active material layer 402 using the graphene 405 isdescribed.

The positive electrode active material particles 404 are made ofsecondary particles having an average diameter or a particle diameterdistribution, which are obtained in such a way that material compoundsarc mixed at a predetermined ratio and baked and the resulting bakedproduct is crushed, granulated, and classified by an appropriate means.Therefore, the shape of the positive electrode active material particles404 is not limited to such a spherical shape as is schematicallyillustrated in FIG. 3C.

The positive electrode active material particles 404 can be made of amaterial into/from which lithium ions can be inserted and extracted. Anexample of the material is a compound that contains lithium and oxygenand has an olivine crystal structure, a layered rock-salt crystalstructure, or a spinel crystal structure.

An example of an olivine-type compound containing lithium and oxygen isa composite oxide represented by LiMPO₄ (general formula) (M is one ormore of Fe(II), Mn(II), Co(II), and Ni(II)). Typical examples of LiMPO₄(general formula) include LiFePO₄, LiNiPO₄, LiCoPO₄, LiMnPO₄,LiFe_(a)Ni_(b)PO₄, LiFe_(a)Co_(b)PO₄, LiFe_(a)Mn_(b)PO₄,LiNi_(a)Co_(b)PO₄, LiNi_(a)Mn_(b)PO₄ (a+b≤1, 0<a<1, and 0<b<c1),LiFe_(c)Ni_(d)Co_(e)PO₄, LiFe_(c)Ni_(d)Mn_(e)PO₄,LiNi_(c)Co_(h)Mn_(e)PO₄ (c+d+e≤1, 0c<1, 0<d<1, and 0<e<1), andLiFe_(f)Ni_(g)Co_(g)Mn_(i)PO₄ (f+g+h+i≤1.0<f<1, 0<g<1, 0<h<1, and0<i<1).

LiFePO₄ is particularly preferable because it properly has propertiesnecessary for the positive electrode active material, such as safety,stability, high capacity density, high potential, and the existence oflithium ions that can be extracted in initial oxidation (charging).

Examples of a layered rock-salt crystal compound containing lithium andoxygen include lithium cobalt oxide (LiCoO₂), LiNiO₂, LiMnO₂, NiCo-basedcompound such as LiNi_(0.8)Co_(0.2)O₂ (general formula:LiNi_(y)Co_(1-x)O₂ (0<x<1)), NiMn-based compound such asLiNi_(0.5)Mn_(0.5)O₂ (general formula LiNi_(x)Mn_(1-x)O₂(0<x<1)),NiMnCo-based compound such as LiNi_(1/3)Mn_(1/3)Co_(1/2)O₂ (alsoreferred to as NMC, general formula: LiNi_(x)Mn_(y)Co_(1-x-y)O₂ (x>0,y>0, x+y<1)), Li(Ni_(0.8)Co_(0.15)Al_(0.05))O₂, and Li₂MnO₃—LiMO₂(M═Co,Ni, or Mn).

LiCo₂ is particularly preferable because of its high capacity, and itsstability in the air and thermal stability higher than those of LiNiO₂.

Examples of a spinel crystal compound containing lithium and oxygeninclude LiMn₂O₄, Li_(1+x)Mn_(2−x)O₄, Li(MnAl)₂O₄, andLiMn_(1.5)Ni_(0.5)O₄.

It is preferable to add a small amount of lithium nickel oxide (LiNiO₂or LiNi_(j−x)MO₂ (M═Co, Al, or the like)) to the spinel crystal compoundcontaining manganese, lithium, and oxygen such as LiMn₂O₄, in which casethe elution of manganese and the decomposition of an electrolytesolution can be suppressed, for example.

A composite oxide expressed by Li(_(2−l))MSiO₄ (general formula) (M isone or more of Fe(II), Mn(II), Co(II), and Ni(II), 0≤j≤2) can also beused as the positive electrode active material. Typical examples of thegeneral formula Li_(2−j))MSiO₄ are Li(_(2−j))FeSiO₄, Li(_(2−j))NiSiO₄,Li(_(2−j))CoSiO₄, Li_(2−j)MnSiO₄, Li(_(2−j))Fe₂Ni₂SiO₄,Li(_(2−j))Fe_(k)Co_(j)SiO₄, Li(_(2−j))Fe₂MnSiO₄,Li_(2−j))Ni_(2−j))Ni₂CoSiO₄, Li(_(2−j))Ni₂Mn₂SiO₄(k+l≤1, 0<k <1, and0<l<1), Li(_(2−j))Fe_(m)Ni_(n)(Co_(q)SiO₄,Li(_(2−j))Fe_(m)Ni_(n)Mn_(q)SiO₄, Li(_(2−j))Ni_(m)Co_(n)Mn_(q)SiO₄(m+n+q ≤1, 0<m−1.0<n<1, and 0<q<1), andLi(_(2−j))Fe_(r)Ni_(s)Co_(t)Mn_(u)SiO₄ (r+s+t+u ≤1, 0<r<1, 0<1.0<t<1,and 0<u<1).

Alternatively, a nasicon compound represented by a general formulaA_(x)M₂(XO₄)₃ (A═Li, Na, or Mg, M═Fe, Mn, Ti, V, Nb, or Al, X═S, P Mo,W, As, or Si) can be used as the positive electrode active material.Examples of the nasicon compound are Fe₂(MnO₄), Fe₂(SO₄)₃, andLi₃Fe₂(PO₄)₃. Further alternatively, a compound represented by a generalformula Li₂MPO₄F, Li₂MP₂O₇, or Li₅MO₄ (M═Fe or Mn), a pecrovskitefluoride such as NaF₃or FeF₃, a metal chaleogenide (a sulfide, aselenide, or a ielluride) such as TiS₂ or MoS₂, a compound containinglithium and oxygen with an inverse spinel crystal structure such asLiMVO₄, a vanadium oxide (V₂O₅, V₆O₁₃, LiV₃O₈, or the like), a manganeseoxide, an organic sulfur, or the like can be used as the positiveelectrode active material.

In the case where carrier ions are alkali metal ions other than lithiumions, or alkaline-earth metal ions, the positive electrode activematerial 404 may contain, instead of lithium in the compound and theoxide, an alkali metal (e.g., sodium or potassium), an alkaline-earthmetal (e.g., calcium, strontium, barium, beryllium, or magnesium).

Although not illustrated, a carbon layer may be provided on a surface ofthe positive electrode active material 404. The carbon layer increasesthe conductivity of an electrode. The positive elect rode activematerial 404 can be coated with the carbon layer by mixing acarbohydrate such as glucose at the time of baking the positiveelectrode active material.

The graphene 405 which is added as a conductive additive to the positiveelectrode active material layer 402 can be formed by reducing grapheneoxide as in the case of producing the negative electrode. Graphene oxidedescribed in Embodiment 1 can be used for the positive electrode activematerial layer 402.

The length of one side (also referred to as a flake size) of thegraphene is greater than or equal to 50 nm and less than or equal, to100 μm, preferably greater than or equal to 800 nm and less than orequal to 20 μm.

As in the cross-sectional view of the positive electrode active materiallayer 402 in FIG. 3C, the plurality of positive electrode activematerial particles 404 are coated with the plurality of graphenes 405.One sheet-like graphene 405 is in contact with the plurality of positiveelectrode active material particles 404. In particular, since thegraphene 405 is in the form of a sheet, surface contact can be made soas to cover part of the surfaces of the positive electrode activematerial particles 404. Unlike a conductive additive in the form ofparticles, such as acetylene black, which makes point contact with apositive electrode active material, the graphene 405 is capable ofsurface contact with low contact resistance; accordingly, the electronconductivity of the positive electrode active material particles 404 andthe graphene 405 can be improved without an increase in the amount ofconductive additive.

Furthermore, surface contact is made between the plurality of graphenes405. This is because graphene oxide with exceptional dispersibility in apolar solvent is used for the formation of the graphenes 405. A solventis removed by evaporation from a polar solvent including graphene oxideuniformly dispersed and the graphene oxide is reduced to graphene;hence, the graphenes 405 remaining in the positive electrode activematerial layer 402 partly overlap with each other and arc dispersed suchthat surface contact is made, thereby forming an electron conductionpath.

Part of the graphene 405 is provided between the positive electrodeactive material panicles 404. The graphene 405 is art extremely thinfilm (sheet t made of a single layer of carbon molecules or stackedlayers thereof and thus is in contact with part of the surfaces of thepositive electrode active material particles 404 so as to trace thesesurfaces. A portion of the graphene 405 that is not in contact with thepositive electrode active material particles 404 is warped between thepositive electrode active material particles 404 and crimped orstretched.

Consequently, the plurality of graphenes 405 form an electron conductionnetwork in the positive electrode 400. This maintains a path forelectric conduction between (he positive electrode active materialpanicles 404. Thus, when graphene oxide is used as a raw material andreduced after the formation of the electrode, graphene as a conductiveadditive is produced. Accordingly, the positive electrode activematerial layer 402 with high electron conductivity can be formed.

The proportion of the positive electrode active material particles 404in the positive electrode active material layer 402 can be increasedbecause if is not necessary to increase the additive amount of aconductive additive to increase contact points between the positiveelectrode active material particles 404 and the graphene 405. This canincrease the discharge capacity of the lithium-ion secondary battery.

The average diameter of a primary particle of the positive electrodeactive material particles 404 is less than or equal to 500 nm,preferably greater than or equal to 50 nm and less than or equal to 500nm. To make surface contact with the plurality of positive electrodeactive material particles 404, the length of a side of the graphene 405is preferably greater than or equal to 50 nm and less than or equal to100 μm, more preferably greater than or equal to 800 nm and less than orequal to 20 μm.

As the binder 406 in the positive electrode active material layer 402,polyvinylidene fluoride (PVDF) is used typically, and polyimide,polytetrafluoroethylene, polyvinyl chloride, ethylene-propylene-dienepolymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber,fluorine rubber, polyvinyl acetate, polymethyl methacrylate,polyethylene, nitrocellulose, or the like can also be used.

The above positive electrode active material layer 402 preferablyincludes the positive electrode active material particles 404 at greaterthan or equal to 00 wt % and less than or equal to 94 wt %, the graphene405 as a conductive additive at greater than or equal to 1 wt % and lessthan or equal to 5 wt %, and the binder at greater than or equal to 1 wt% and less than or equal to 5 wt % with respect to the total weight ofthe positive electrode active material layer 402.

As a separator included in the lithium-ion secondary battery, a porousinsulator such as cellulose, polypropylene (PP), polyethylene (PH),polybutene, nylon, polyester, polysulfone. polyacrylonitrile,polyvinylidene fluoride, or tetrafluoroethylene can be used.Alternatively, non woven fabric of a glass fiber or the like, or adiaphragm in which a glass fiber and a polymer fiber are mixed may beused.

The electrolytic solution used in the lithium-ion secondary battery ispreferably a nonaqueous solution (solvent) containing an electrolyte(solute).

As a solvent for the electrolytic solution, an aprotic organic solventis preferably used. For example, one of ethylene carbonate (EC),propylene carbonate (PC), butylene carbonate, cbloroethylene carbonate,vinylene carbonate, γ-butyrolactone, γ-valerolactone, dimethyl carbonate(DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methylformate, methyl acetate, methyl butyrate, 1,3-dioxane, 1,4-dioxane,dimethoxyethane (DME), dimethyl sulfoxide, diethyl ether, methyldiglyme, acetonitrile, benzomtrile, tetrahydrofuran, sulfolane, andsultone can be used, or two or more of these solvents can be used incombination in an appropriate ratio.

When a gelled high-molecular material is used as the solvent for theelectrolytic solution, safety against liquid leakage and the like isimproved. Furthermore, a thinner and more lightweight lithium-ionsecondary battery can be obtained. Typical examples of the gelledhigh-molecular material include silicone gel, acrylic gel, acrylonitrilegel, polyethylene oxide, polypropylene oxide, and a fluorine-basedpolymer.

Alternatively, the use of one or more of ionic liquids (room temperaturemolten salts) that have non-flarnmability and non*volatility as thesolvent for the electrolytic solution can prevent a lithium-ionsecondary battery from exploding or catching fire even when thelithium-ion secondary battery internally shorts out or the internaltemperature increases due to overcharging or the like. Thus, thelithium-ion secondary battery has improved safety. With the use of theionic liquid as the solvent for the electrolytic solution, thelithium-ion secondary battery can favorably operate even in a lowtemperature range (sub-zero temperature range) us compared with the casewhere an organic solvent is used us the solvent for the electrolyticsolution.

As an electrolyte dissolved in the above solvent, one of lithium saltssuch as LiPF₆, LiClO₄ , LiAsF₆, LiBF₄, LiAlCl₄, LiSCN, LiBr, LiI,LiI₂SO₄, Li₂B₁₀Cl₁₀, Li₂B₁₂Cl₁₂, LiCF₃SO₃, LiC₄F₉SO₃, LiC(CF₃SO₂)₃),LiC(C₃F₄SO₂)₃), LiN(CF₃SO₂)₂, LiN(C₄F₉SO₂) (CF₃SO₂), and LiN(C₂F₅SO₂)₂can be used, or two or more of these lithium salts can be used incombination in an appropriate ratio.

Although lithium ions are used as carrier ions in the above electrolyte,other carrier ions can also be used. When carrier ions other thanlithium ions are alkali metal ions or alkaline-earth metal ions, insteadof lithium in the above lithium salts, an alkali metal (e.g., sodium orpotassium), an alkaline-earth metal (e.g., calcium, strontium, barium,beryllium, or magnesium) may be used for an electrolyte.

Instead of the electrolytic solution, a solid electrolyte including aninorganic material such as a sulfide-based inorganic material or anoxide-based inorganic material, or a solid electrolyte including amacromolecular material such as a polyethylene oxide (PEO)-basedmacromolecular material may alternatively be used. When the solidelectrolyte is used, a separator is not necessary. In addition, thebattery can be entirely solidified, and thus there is no possibility ofliquid leakage to increase the safety of the battery.

Next, a structure of a lithium-ion secondary battery will be describedwith reference to FIGS. 4A to 4C.

FIG. 4A is an external view of a coin-type (single-layer fiat type)lithium-ion secondary battery, part of which illustrates across-sectional view of the coin-type lithium-ion secondary battery.

In a coin-type lithium-ion secondary battery 550, a positive electrodecan 551 serving also as a positive electrode terminal and a negativeelectrode can 552 serving also as a negative electrode terminal areinsulated and sealed with a gasket 553 made of polypropylene or thelike. A positive electrode 554 includes a positive electrode currentcollector 555 and a positive electrode active material layer 556 whichis provided in contact with the positive electrode current collector555. A negative electrode 557 includes a negative electrode currentcollector 558 and a negative electrode active material layer 559 which:is provided in. contact with the negative electrode current collector558. A separator 560 and. an. electrolytic solution (not illustrated)are provided between the positive electrode active material layer 556and the negative electrode active material layer 559.

The negative electrode 557 includes the negative electrode activematerial layer 559 over the negative electrode current collector 558.The positive electrode 554 includes the positive electrode activematerial layer 556 over the positive electrode current collector 555.

The positive electrode 554, the negative electrode 557, the separator560, and the electrolytic solution can be formed using the abovedescribed members.

For the positive electrode can 551 and the negative electrode can 552 amend having corrosion resistance to an electrolytic solution, such asnickel, aluminum, or titanium, an alloy of such a metal, or an alloy ofsuch a metal and another rectal (e.g., stainless steel) can be used.Alternatively, the positive electrode can 551 and the negative electrodecan 552 are preferably covered with nickel, aluminum, or the like inorder to prevent corrosion caused by the electrolytic solution. Thepositive electrode can 551 and the negative: electrode can 552 areelectrically connected to the positive electrode 554 and the negativeelectrode 557, respectively.

The negative electrode 557, the positive electrode 554, and theseparator 560 are immersed in the electrolytic solution. Then, asillustrated in FIG. 4A, the positive electrode can 551, the positiveelectrode 554, the separator 560, the negative electrode 557, and thenegative electrode can 552 are stacked in this order with the positiveelectrode can 551 positioned at the bottom, and the positive electrodecan 551 and the negative electrode can 552 are subjected to pressurebonding with the gasket 553 interposed therebetween. In such a manner,the coin-type lithium-ion secondary battery 550 is fabricated.

It is preferable that, for example, a graphite electrode (black leadelectrode) and lithium iron phosphate (LiFePO₄) be used for the negativeelectrode 557 and an active material of the positive electrode 554 ofthe lithium-ion secondary battery 550, respectively.

Next, an example of a laminated lithium-ion secondary battery will bedescribed with reference to FIG. 4B. In FIG. 4B, the inside of thelaminated lithium-ion secondary battery is partly exposed forconvenience.

A laminated lithium-ion secondary battery 570 illustrated in FIG. 4Bincludes a positive electrode 573 including a positive electrode currentcollet tor 571 and a positive electrode active material layer 572, anegative electrode 576 including a negative electrode current collector574 and a negative electrode active material layer 575, a separator 577,electrolytic solution (not illustrated), and an exterior body 578. Theseparator 577 is provided between the positive electrode 573 and thenegative electrode 576 in the exterior body 578. The exterior body 578is filled with the electrolytic solution. Although the one positiveelectrode 573, the one negative electrode 576, and the one separator 577are used in FIG. 4B the lithium-ion secondary battery, may have alayered structure in which positive electrodes and negative electrodesare alternately stacked and separated by separators.

The positive electrode, the negative electrode, the separator, and theelectrolytic solution (an electrolyte and a solvent) can be formed usingthe above-described members.

In the laminated lithium-ion secondary battery 570 illustrated in FIG.4B, the positive electrode current collector 571 and the negativeelectrode affront collector 574 also serve as terminals tabs) for anelectrical contact with an external portion. For this reason, each ofthe positive electrode cu rent collector 571 and the negative electrodecurrent collector 574 is arranged so as to be partly exposed on theoutside of the exterior body 578.

As the exterior body 578 in the laminated lithium-ion secondary battery570, for example, a laminate film having the following three-layerstructure can be used: a highly flexible mend thin film of aluminum,stainless steel, copper, nickel, or the like is provided over a filmformed of a material such as polyethylene, polypropylene, polycarbonate,ionomer, polyamide, and an insulating synthetic resin film of apolyaramde-based resin, a polyester-based resin, or the like is providedas the outer surface of the exterior body over the metal thin film. Withsuch a three-layer structure, permeation of the electrolytic solutionand a gas can be blocked and an insulating property and resistance tothe electrolytic solution can be obtained.

Next, an example of a rectangular lithium-ion secondary battery will bedescribed with reference to FIG. 4C. A wound body 580 illustrated inFIG. 4C includes a negative electrode 581, a positive electrode 582, anda separator 583. The wound body 580 is obtained by winding a sheet of astack in which the negative electrode 581 overlaps with the positiveelectrode 582 with the separator 583 provided therehetween. The woundbody 580 is covered with a rectangular sealing can or the like, thus, arectangular lithium-ion secondary battery is fabricated. Note that thenumber of stacks each including the negative electrode 581, the positiveelectrode 582, and the separator 583 may be determined as appropriatedepending on required capacity and the volume of a battery.

As in a cylindrical lithium-ion secondary battery, the negativeelectrode 581 is connected to a negative electrode lab (not illustrated)through one of a terminal 584 and a terminal 585, and the positive.electrode 582 is connected to a positive electrode tab not illustrated)through the other of the terminals 584 and 585.

Although the coin-type, laminated, and rectangular lithium-ion secondarybatteries are described above, lithium-ion secondary batteries withother variety of shapes can also be used. Furthermore, a plurality ofpositive electrodes, a plurality of negative electrodes, and a pluralityof separators may be stacked or wound.

By using the electrode for a lithium-ion secondary battery of oneembodiment of the present invention as the negative electrode of thelithium-ion secondary battery, the capacity of the lithium-ion secondarybattery cart be increased.

The electrode (negative electrode) for a lithium-ion secondary batteryof one embodiment of the present invention uses silicon and thereforehas large capacity. Accordingly, the thickness the negative electrodeactive material layer can be reduced to increase the thickness of thepositive electrode active material layer. In other words, the amount ofpositive electrode active material can be increased, resulting in anincrease in the energy density of the lithium-ion secondary battery.

This embodiment can be implemented in appropriate combination with anyof the other embodiments.

Embodiment 3

The lithium-ion secondary battery of one embodiment of the presentinvention can be used for power supplies of a variety of electricdevices operated with electric power.

Specific examples of electric devices each utilizing the lithium-ionsecondary battery of one embodiment of the present invention are asfollows: display devices of televisions, monitors, and the like,lighting devices, desktop personal computers and laptop personalcomputers, word processors, image reproduction devices which reproducestill images or moving images stored in recording media such as digitalversatile discs (DVDs), portable compact disc (CD) players, radioreceivers, tape recorders, headphone stereos, stereos, clocks such astable clocks and wall clocks, cordless phone handsets, transceivers,cellular phones, ear phones, portable game machines, calculators,portable information terminals, electronic notebooks, e-hook readers,electronic translators, audio input devices, cameras such as digitalstill cameras and video cameras, toys, electric shavers, high-frequencyheating appliances such as microwave ovens, electric rice cookers,electric washing machines, electric vacuum cleaners, water heaters,electric fans, hair dryers, air-conditioning systems such as airconditioners, humidifiers, and dehumidifiers dishwashers, dish dryers,clothes dryers futon dryers, electric refrigerators, electric freezers,electric refrigerator-freezers, freezers for preserving DNA,flashlights, electric power tools such as chain saws, smoke detectors,and medical equipment such as dialyzers. Further examples are asfollows: industrial equipment such as guide lights, traffic lights, beltconveyors, elevators, escalators, industrial robots, power storagesystems, and power storage devices for leveling the amount of powersupply and smart grid. In addition, moving objects driven by electricmotors using electric power from the lithium-ion secondary batteries arealso included in the category of electric devices. Examples of themoving objects include electric vehicles (EV), hybrid electric vehicles(HEV) which include both an internal-combustion engine and a motor,plug-in hybrid electric vehicles (PHEV), tracked vehicles in whichcaterpillar tracks are substituted for wheels of these vehicles,motorized bicycles including motor-assisted bicycles, motorcycles,electric wheelchairs, golf carts, boats, ships, submarines, helicopters,aircraft, rockets, artifical satellites, space probes, planetary probes,and spacecrafts.

In the electric devices, the lithium-ion secondary battery of oneembodiment of the present invention can be used as a main power supplyfor supplying enough electric power for almost the whole powerconsumption. Alternatively, in the electric devices, the lithium-ionsecondary battery of one embodiment of the present invention can be usedas an uninterruptible power supply which can supply electric power tothe electric devices when the supply of electric power from the mainpower supply or a commercial power supply is stopped. Stillalternatively, in the electric devices, the lithium-ion secondarybattery of one embodiment of the present invention can be used as anauxiliary power supply for supplying electric power to the electricdevices at the same time as the power supply from the main power supplyor a commercial power supply.

A portable terminal which is an example of electric devices is describedwith reference to FIGS. 5A to 5C.

FIGS. 5A and 5B illustrate a foldable tablet terminal 650. FIG. 5Aillustrates the tablet terminal unfolded. The tablet terminal 650includes a housing 651, a display portion 652 a, a display portion 652b, a display mode switching button 653, a power switch 054, apower-saving mode switching button 655 and an operation switch 656.

Part of the display portion 652 a can be a touch panel area 657 a, anddata can be input by touching operation keys 658 displayed. Although ahalf region in the display function, the display portion 652 a is notlimited to this structure. The whole region in the display portion 652 amay have a touch panel function. For example, the display portion 652 acan display keyboard buttons in the whole region to be a touch panel,and the display portion 052 b can be used as a display screen.

A touch panel area 057 b can be provided in part of the display portion652 b like in the display portion 652 a. When a keyboard displayswitching button 659 displayed on the touch panel is touched with afinger, a stylus, or the like, a keyboard can be displayed on thedisplay portion 651 b.

Both the touch panel area 657 a and the touch panel area 657 b can becontrolled by touch input at the same time.

A semiconductor display device such as a liquid crystal display device,a light-emitting device including pixels each provided with alight-emitting element such as an organic EL element, an electrophoresisdisplay device, a digital micromirror device (DMD), a plasma displaypanel (PDP), or a field emission display (FED) can be used for thedisplay portions 652 a and 65 b.

The display mode switching button 653 allows switching between alandscape mode and a portrait mode, or between color display andblack-and-white display. For example. The power-saving mode switchingbutton 655 allows optimizing the display luminance in accordance withthe amount of external light in use which is detected by an opticalsensor incorporated in the tablet terminal. In addition to the opticalsensor, other detecting devices such as sensors for determininginclination, such as a gyroscope or an acceleration sensor, may beincorporated in the tablet terminal.

Although the display portions 652 a and 652 b have the same display areain FIG. 5A, one embodiment of the present invention is not particularlylimited thereto. The display portions 652 a and 652 b may have differentdisplay areas, and may also have different display qualities. Forexample, one of the display portions 652 a and 652 b may display higherdefinition images than the other.

FIG. 5B illustrates the tablet terminal 650 closed. The tablet terminal650 includes the housing 651, a solar cell 660, a charge/dischargecontrol circuit 670, a battery 671, and a DC-DC converter 672. In FIG.5B, the charge/discharge control circuit 670 includes the battery 671and the DC-DC converter 672 as an example. The lithium-ion secondarybattery described in the above embodiments is used as the battery 671.

Since the tablet terminal 650 can be folded, the housing 651 can beclosed when the tablet terminal is not in use. Thus, the displayportions 652 a and 652 b can be protected, which permits the tabletterminal 650 to have high durability and improved reliability forlong-term use.

The tablet terminal illustrated in FIGS. 5A and 5B can also havefunction of displaying various kinds of data (e.g., a still image, amoving image, and a text image), a function of displaying a calendar, adate, the time, or the like on the display portion, a touch-input, afunction of operating or editing data displayed on the display portionby touch input, a function of controlling processing by various kinds ofsoftware (programs), and the like.

The solar cell 660, which is attached on a surface of the tabletterminal, can supply electric power to a touch panel, a display portion,an image signal processor, and the like. Note that the solar cell 660can be provided on one or both surfaces of the housing 651 and thus thebattery 671 can be charged efficiently. The use of the lithium-ionsecondary battery of one embodiment of the present invention as thebattery 671 has advantages such as a reduction in size.

The structure and operation of the charge/discharge control circuit 670illustrated in FIG. 5B will be described with reference to a blockdiagram of FIG. 5C. FIG. 5C illustrates the solar cell 660, the battery671, the DC-DC converter 672, a converter 673, switches SW1 to SW3, andthe display portion 652. The battery 671, the DC-DC converter 672, theconverter 673, and the switches SW1 to SW3 correspond so thecharge/discharge control circuit 670 in FIG. 5B.

First, an example of the operation where electric power is generated bythe solar cell 600 using external light will be described. The voltageof electric power generated by the solar cell 660 is raised or loweredby the DC-DC converter 672 so that the electric power has a voltage forcharging the batter 671. When the display portion 652 is operated withthe electric power from the solar cell 660, the switch SW1 is turned onand the voltage of the electric power is raised or lowered by theconverter 673 to a voltage needed for operating the display portion 652.When display on the display portion 652 is not performed, the switch SW1is turned off and the switch SW2 is turned on so that the battery 671may be charged.

Although the solar cell 600 is described as an example of a powergeneration means, there is no particular limitation on the powergeneration means, and the battery 671 may be charged with any of theother means such as a piezoelectric element or a thermoelectricconversion element (Peltier element). For example, the battery 671 maybe charged with a non-contact power transmission module capable ofperforming charging by transmitting and receiving electric powerwirelessly (without contact), or any of the other charge means used incombination.

It is needless to say that one embodiment of the present invention isnot limited to the electric device illustrated in FIGS. 5A to 5C as longas the electric device is equipped with the lithium-ion secondarybattery described in the above embodiments.

EXAMPLE 1

In this example, the electrode for a lithium-ion secondary battery shownin Embodiment 1 was fabricated and observed by scanning electronmicroscope (SEM). Then, the charge-discharge characteristics of ahalf-cell including the electrode were measured to obtain thecharge-discharge efficiency of the half-cell.

The lithium-ion secondary battery used in this example was fabricated bythe method shown in the flowchart of FIG. 1.

In this example, a negative electrode includes a negative electrodecurrent collector made of 18-μm-thick copper foil. Silicon particles(with an average diameter of 60 nm) as a negative electrode activematerial, graphene oxide as a conductive additive, and a polyimideprecursor as a binder were mixed at a ratio of 40:40:20 (weight %). Morespecifically, 0.12 g of silicon panicles, 0.12 g of graphene oxide, and0.2 g of undiluted polyimide were mixed. Note that the undilutedpolyimide used in this example contains 30 wt % of solid content(polyimide precursor) and 70 wt % of solvent (NMP). Therefore, theweight of polyimide imidized after a heating process is 0.06 g (0.2g×0.3). The mixture of the polyimide precursor and NMP has a pH ofapproximately 3.

As shown in step S11 in FIG. 1, the active material, the binder, andgraphene oxide were mixed to prepare slurry. The slurry was prepared inthe following manner: first, silicon panicles and NMP as a polar solventwere mixed; next, graphene oxide and NMP were added to the mixture ofsilicon particles and NMP; then, a polyimide precursor was added to themixture of silicon particles, graphene oxide, and NMP; lastly, NMP wasadded to that mixture until the mixture has predetermined viscosity andNMP and the mixture were mixed. After that, the slurry was left in theair for a day (approximately 24 hours).

Then, as shown in step S12, the prepared slurry was applied to copperfoil. The application of the slurry was performed in the followingmanner: copper foil was set in a coating device and slurry was droppedonto the copper foil; then, a doctor blade (with a gap of 100 μm) wasplaced in the point where the slurry was dropped and the blade was movedby the coating device.

Next, as shown in step S13, the slurry was dried. The copper foil coatedwith the slurry was set in a forced-air dryer and dried at 80° C. fortwo hours. In this manner, an electrode with the dried slurry wasobtained.

Then, as shown in step S14, the electrode with the dried slurry wasbaked in a vacuum furnace. The temperature in the vacuum furnace startedto increase after the degree of vacuum in the vacuum furnace reached2×10⁻² [Pa].

The electrode the dried slurry was baked at temperatures graduallyincreasing to the maximum temperature of the vacuum furnace. First, thetemperature was raised from room temperature to 120° C. and baking wasperformed for one hour; then, the temperature was raised from 120 to200° C. and baking was performed for 10 minutes; next, the temperaturewas raised from 200° C. to 250° C. and baking was performed for onehour; lastly, the temperature was raised from 250° C. 372° C. and bakingwas performed for 30 minutes. Note that the degree of vacuum in thevacuum furnace reached approximately 1×10⁻⁶ [Pa] in the baking.

The electrode that had been baked was observed by SEM. FIG. 6 shows aSEM photogram of the electrode fabricated in this example.

The SEM photograph of FIG. 6 shows that a nanowire grows with a siliconparticle used as a nucleus and extends in one direction into a fineneedle. Nanowires are tangled, so that a network of nanowires isobtained. Furthermore, graphene is formed over the tangled nanowires.The graphene has a planar shape, and thus the surface contact with thetangled nanowires was observed.

The photograph of FIG. 6 indicates that the electrode for a lithium-ionsecondary battery of one embodiment of the present invention can befabricated.

Next, a half-cell was produced using the electrode of this example. Themeasurement results of the charge-discharge characteristics andcharge-discharge efficiency of the half-cell will be described.

The half-cell produced in this (this example includes metal lithium as apositive electrode and the electrode produced in this example as anegative electrode. In the fabrication of the half-cell manufactured byNIPPON TOMUSERU was used.

An electrolyte solution was formed by dissolving lithiumhexafluorophosphate (LiPF₆) in a solution where ethylene carbonate (EC)and diethyl carbonate (DEC) were mixed at a ratio of 1:1. As aseparator, polypropylene was used.

The charge-discharge characteristics of the half-cell produced in thisexample were measured in the following conditions. Charge and dischargein the first cycle were performed at a rate of 0.1 C (it takes 10 hoursfor charging), and charge and discharge in the second and the subsequentcycles were performed at a rate of 1 C (it takes 1 hour for charging).In every 20 cycles, charge and discharge were performed at a rare of 0.1C (it takes 10 hours for charging). The charge and discharge wereperformed 180 cycles to measure the discharge rapacity. The charge anddischarge were performed with a constant current at voltages rangingflora 0 V to 1 V and an environmental temperature of 25° C.

The charge-discharge efficiency was obtained From the charge-dischargecharacteristics of the half-cell; as a result, the charge-dischargeefficiency in 180-cycle charge and discharge was found to be 99.22 onaverage. This is probably because the nanowires prevented a decrease inthe charge-discharge characteristics due to silicon deformation andbreakage.

The above results revealed that the electrode for a lithium-ionsecondary battery of one embodiment of the present invention had highreliability and that a lithium-ion battery including the electrode hadimproved charge-discharge efficiency.

This application is based on Japanese Patent Application serial No.2013-166809 filed with Japan Patent Office on Aug. 9, 2013 the entirecontents of which are hereby incorporated by reference.

1. (canceled)
 2. A method for manufacturing a lithium-ion storagebattery comprising: providing a negative electrode adjacent to apositive electrode, wherein the positive electrode comprises a positiveelectrode current collector and a positive electrode active materiallayer, wherein the negative electrode comprises a negative electrodecurrent collector and a negative electrode active material layer,wherein the negative electrode active material layer comprises siliconparticles and a binder, wherein a silicon wire is formed from a firstpart of the silicon particles by heating after forming the negativeelectrode active material layer, wherein the silicon particles have anaverage diameter of 10 nm to 1□ m before the heating, and wherein athickness of the negative electrode active material layer is smallerthan a thickness of the positive electrode active material layer.
 3. Amethod for manufacturing a lithium-ion storage battery comprising:providing a negative electrode adjacent to a positive electrode, whereinthe positive electrode comprises a positive electrode current collectorand a positive electrode active material layer, wherein the negativeelectrode comprises a negative electrode current collector and anegative electrode active material layer, wherein a method formanufacturing the negative electrode active material layer comprises:mixing a first mixture comprising silicon particles and graphene oxide,a polyimide precursor and a solvent to form a slurry; and applying theslurry over the negative electrode current collector and heating,wherein the heating forms a nanowire using a first part of the siliconparticles, reduces the graphene oxide to graphene, and imidizes thepolyimide precursor to polyimide, and wherein the nanowire grows with asecond part of the silicon particles used as a nucleus and extends intoa needle by the heating.
 4. The method for manufacturing the lithium-ionstorage battery according to claim 2, wherein the binder is polyimide,wherein a precursor of polyimide is used for forming the negativeelectrode active material layer, and wherein the precursor of polyimideis imidized by the heating.
 5. The method for manufacturing thelithium-ion storage battery according to claim 2, wherein the siliconwire has a length of ten micrometers or more.
 6. The method formanufacturing the lithium-ion storage battery according to claim 2,wherein a second part of the silicon particles forms a first aggregatedobject by the heating.
 7. The method for manufacturing the lithium-ionstorage battery according to claim 6, wherein the silicon wire growswith the first aggregated object as a nucleus.
 8. The method formanufacturing the lithium-ion storage battery according to claim 7,wherein a third part of the silicon particles forms a second aggregatedobject by the heating, and wherein the silicon wire is attached to thesecond aggregated object after the heating.
 9. The method formanufacturing the lithium-ion storage battery according to claim 2,wherein the heating is performed at a temperature equal to or less than400□ C.
 10. The method for manufacturing the lithium-ion storage batteryaccording to claim 2, wherein the heating is performed at a temperatureequal to or greater than 360□ C and equal to or less than 400□ C. 11.The method for manufacturing the lithium-ion storage battery accordingto claim 2, wherein the negative electrode active material layercomprises a conductive additive.
 12. The method for manufacturing thelithium-ion storage battery according to claim 2, wherein the negativeelectrode active material layer comprises graphene and polyimide. 13.The method for manufacturing the lithium-ion storage battery accordingto claim 2, wherein the positive electrode active material layercomprises graphene and polyvinylidene fluoride.
 14. The method formanufacturing the lithium-ion storage battery according to claim 3,wherein a thickness of the negative electrode active material layer issmaller than a thickness of the positive electrode active materiallayer.
 15. The method for manufacturing the lithium-ion storage batteryaccording to claim 3, wherein the silicon particles have an averagediameter of 10 nm to 1□ m before the heating.
 16. The method formanufacturing the lithium-ion storage battery according to claim 3,wherein the nanowire has a length of ten micrometers or more.
 17. Themethod for manufacturing the lithium-ion storage battery according toclaim 3, wherein the heating is performed at a temperature equal to orgreater than 360□ C and equal to or less than 400□ C.
 18. The method formanufacturing the lithium-ion storage battery according to claim 3,wherein the positive electrode active material layer comprises grapheneand polyvinylidene fluoride.